Citric Acid-Modified Fenton s Reaction for the Oxidation of Chlorinated Ethylenes

Transcription

1 Citric Acid-Modified Fenton s Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems Yongkoo Seol* and Iraj Javandel Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA * Corresponding Author: Current Affiliation: US DOE National Energy Technology Laboratory, Morgantown, WV Tel: 304) Fax: 304) yongkoo.seol@netl.doe.gov

2 Citric Acid-Modified Fenton s Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems Yongkoo Seol and Iraj Javandel Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA Abstract Fenton s reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton s reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton s reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H 2 O 2 concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H 2 O 2 relative to iron catalysts (Fe 2+ /H 2 O 2 < 1/330) would result in lowering the efficiency of contaminant removal by iron chelations in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

3 46 Key Words: Fenton s reaction, citric acid, hydrogen peroxide, organic contaminant Introduction Contamination of soil and groundwater by chlorinated hydrocarbons imposes significant threats to water resources and public health. One of the techniques used to remediate chlorinated hydrocarbon contamination in soil and groundwater is in situ chemical oxidation with Fenton s reagent. Ferrous iron and H 2 O 2 are injected into an acidic subsurface system to decompose contaminants in place. Normally, H 2 O 2 is a relatively low-activity oxidant. However, under acidic conditions (ph = 3 to 5), Fe 2+ dissociates H 2 O 2 to form unstable and highly reactive hydroxyl radicals ( OH), as shown in Eq. 1, which actively mineralize organic contaminants (C a H b X c ) into CO 2, water, and inorganic salts, (Eq. 2; Walling, 1975; Sun and Pignatello, 1992). The Fe 2+ is then catalytically regenerated by the Fe 3+ reaction with H 2 O 2 (Eq. 3). Fe 2+ + H 2 O 2 Fe 3+ + OH + OH (1) C a H b X c + Fe 2+ + xh 2 O 2 Fe 3+ + cx +aco 2 + 2H 2 O + bh + (2) Fe 3+ + H 2 O 2 Fe 2+ +H + + HO 2 (3) Under less acidic conditions (ph > 6), the iron catalyst precipitates as Fe(OH) 3, and instead of generating the hydroxyl radical, the H 2 O 2 decomposes into oxygen, water, and heat, which can create hazardous operation condition. Therefore, it is critical to provide proper acidic conditions to achieve optimum and safe decontamination when Fenton s reaction is employed (Walling 1975; Hickey et al., 1995).

4 Recent studies on Fenton s reaction are concentrated on improving the remediation technique by minimizing the addition of extrinsic materials into subsurface systems and by using environmentally benign chemicals. Deliverability of natural iron catalyst as a means of minimizing the extrinsic chemical addition was examined extensively by many researchers (Ravikumar and Gurol, 1994; Kong et al., 1998; Watts et al., 1999; Teel et al., 2001; Kwan and Voelker, 2002; Teel and Watts, 2002), and showed that H 2 O 2 could initiate Fenton s reaction in the presence of naturally occurring iron minerals, such as goethite and magnetite in soil. Those studies proved that an ironmineral-catalyzed H 2 O 2 system could be successfully applied to field problems under acidic conditions when soils contain 0.5 to 5 wt% of iron minerals The Fenton s reactions for degradation of organic compounds have also been studied in the presence of naturally-occurring organic acids, such as humic and fulvic acids (Voelker and Sulzberer, 1996; Paciolla et al., 1999). Organic acids contain a high density of functional groups, which can conjugate metal ions to form ion complexes. The acids can affect the effectiveness of Fenton s reaction by providing an iron source and by creating proximity between the catalytic iron and organic contaminants for the reaction (Lindsey et al., 2003). Paciolla et al. (1999) confirmed that iron-sorbed humic acid produces OH through the reaction with H 2 O 2. Complexes of Fe 2+ -fulvic acid increase the Fenton s reaction rate at ph = 5, consuming more H 2 O 2 than without fulvic acid (Voelker and Sulzberger, 1996). Sun and Pignatello (1992) examined the oxidation of 2,4- dichlorophenoxyaetic acid (2,4-D) with H 2 O 2 and Fe 3+ chelated to various organic acids at ph = 6, and showed that when Fe 3+ forms chelate with organic acid, the chelated Fe 3+ was more active in generating OH and decomposing 2,4-D than the precipitated Fe 3+.

5 This study investigates whether Fenton s reaction can be initiated by using an organic acid such as citric acid, a food-grade substance, instead of sulfuric acid as an acidifying agent. Citric acid is biodegradable and, when injected into subsurface systems, it could be nutrients for microbes participating in biodegradation of contaminants, as well as an acidifying agent for the chemical oxidation. Citric acid makes a ph buffer at ph = 3 (pk a = 3.08), at which Fenton s reaction actively occurs. Citric acid has a strong ability to chelate metal ions and keep them in solution at those values of ph where the metals would otherwise precipitate (Li et al., 2005). Citric acid, however, can adversely affect the effectiveness of Fenton s reaction. Citric acid can inhibit organic compound decomposition by scavenging the OH (Voelker and Sulzberger, 1996) and by separating the OH formation sites from the pollutants (Lindsey and Tarr, 2000) The objectives of this study are to evaluate the applicability of citric acid as an acidifying agent for Fenton s reagent and to ascertain optimum conditions for effective citric-acid modified Fenton s reagent as an organic contaminant decomposing technique Experimental Procedures Chemicals and Analyses Bench-scale experiments were performed to evaluate the effectiveness of Fenton s oxidation for remediating soils contaminated with chlorinated ethylenes, including trichloroethylene (TCE), tetrachloroethylene (PCE), and cis 1,2- dichloroethylene (DCE) (98%, Aldrich, Milwaukee, WI.). The organic compound concentrations in liquid and soil were measured using a GC-MS, using EPA Method

6 B, by an EPA certified laboratory. Various concentrations (3%, 15%, 30%, and 50%) of H 2 O 2 solutions (EMD Chemicals, Gibbstown, NJ.) were used for a possible range of H 2 O 2 injection. Citric acid (2-Hydroxy-1,2,3-propanetricarboxylic acid) and sulfuric acid stock solution were prepared at concentrations of 0.5 M and 1.0 N, respectively. Iron sulfate salt (FeSO 4 7H 2 O) was used as a source of Fe 2+. A silty clay soil was collected for this study from the campus of Lawrence Berkeley National Laboratory near Building 51L. The sample was air-dried and sieved through a 2-mm mesh before use. Soil characteristics are listed in Table 1. Sorption coefficients in the table were measured for the selected soil assuming linear sorption Batch Experiments Batch tests were conducted to examine whether or not Fenton s oxidation decompose the organic compound in the aqueous solutions with 12 combinations of three acidifying agents (sulfuric acid, citric acid, and deionized water) and four iron sources (FeSO 4, filtered soil solution, soil, and no iron). The 12 acidified solutions were prepared by diluting two concentrated acid solutions (sulfuric acid and citric acid) and deionized water as a control, with FeSO 4 solution (50 mg Fe 2+ L -1 ) for one set and deionized water for three sets. While one set was further diluted by FeSO 4 solutions, the other three sets of the deionized water-diluted solutions were mixed with (1) deionized water for a control (no iron), (2) acid solutions with the soil sample (2 g) as an iron catalyst source, and (3) filtered soil solutions, respectively The filtered soil solutions were prepared by mixing 15 g of soil with 150 ml of the diluted sulfuric acid solution, citric acid solutions, and deionized water separately on a mechanical shaker overnight, and by filtering the supernatants of the soil solutions with 0.45 μm filters. In order to make consistent organic compound concentrations, a

7 concentrated organic compound aqueous solution (PCE, TCE, and DCE) was prepared and spiked into the 12 acidified solution sets described above with different acids and iron sources. Each 12-acidified solution batch had 5 subsets for varying H 2 O 2 concentration (0 to 4% H 2 O 2 ). The final volume of each acidified solution was about 25 ml including 2 ml of H 2 O 2 solutions. There was no head space left in 25 ml reaction bottles Final concentrations of acids in the acidified solutions were 24 mn for citric acid and 16 mn for sulfuric acid. The ph values of the acidified solutions were near 3 while the control solutions without acid had a ph value of about 7. Final organic compound concentrations ranged from 800 to 1200 μgl -1 for the three contaminants Reactions were allowed to continue for more than 24 h at 4 ºC under dark conditions. The sample bottles were visually observed to ascertain reactions occurring and to identify reaction products before instrumental analysis Column Experiments The column experiments similarly involved the two different acid solutions (sulfuric acid, and citric acid) and a control solution without acid. Soil samples of 160 g were packed in three glass columns (2.5 cm diameter 15 cm length). The soil columns were treated in three steps: (1) wetting and contaminant emplacement with an organic compound solution, (2) acidification with the three acid solutions (sulfuric acid, citric acid, and control) spiked with organic compounds, (3) H 2 O 2 injection for organic compound decomposition. A 10-pore volume (10 25 ml) of an organic compound stock solution (PCE, TCE, and DCE, μg L -1 ) was flushed through the columns in a rate of 0.5 ml min -1 to uniformly wet the columns and to emplace the

8 organic compounds thoroughly. The organic compound stock solution for the column experiment was prepared with a CaCl 2 solution (0.005 M CaCl 2 with FeSO 4, 50 mg Fe 2+ L -1 ), instead of deionized water, in order to prevent soil dispersion. The volume of the organic compound solutions injected for the contaminant emplacement was determined by the retardation factors ( 3.0), which were calculated based on the sorption coefficients estimated in preliminary measurements (Table 1) and an assumed soil organic carbon content (0.5%), so that the organic compound concentrations in the column would be uniform throughout the column In order to acidify the soil, each contaminated soil columns was additionally injected with 1 pore volume (25 ml) of citric acid solution (CA; 0.5 M citric acid with FeSO 4, 50 mg Fe 2+ L -1 ), sulfuric acid solution (SA; 1 N sulfuric acid with FeSO 4, 50 mg Fe 2+ L -1 ), and CaCl 2 solution (0.005 M CaCO 3 with FeSO 4, 50 mg Fe 2+ L -1 ) as a control, respectively. Each of there three solutions had the same concentration of organic compounds. The concentrations of the acid solutions were predetermined to have column soil solutions of ph = 3, only for sulfuric acid and citric acid. The organic compound concentrations in the injected acid solutions were the same as the concentration in the initial organic compound stock solution As a final step, one pore volume of 3% H 2 O 2 solution (30% stabilized H 2 O 2 diluted with deionized water, FeSO 4 added) was injected into each acidified columns (CA and SA), while the same volume of CaCl 2 solution was injected into the control column. Liquid and gas effluent were collected separately with tedlar bags for the first one hour, after which the columns were closed and kept in a refrigerator. Similar to batch tests, H 2 O 2 reactions inside the columns were allowed to proceed for 24 h before the columns

9 were opened for soil sampling and contaminant analysis. Liquid samples from the tedlar bags and soil samples collected from the glass columns were directly analyzed for organic compound concentrations, whereas, due to limited gas volume collected, the organic compound concentrations in the gas samples were calculated using the measured concentrations of liquid in the effluent bag based on Henry s constant. Mass balance of organic compounds was calculated to demonstrate the removal efficiency of the organic compounds with H 2 O 2 injections Results and Discussion Batch Experiments Batch samples were visually observed to examine the occurrence of reaction products and gas accumulation resulting from the Fenton s reaction. H 2 O 2 added to sulfuric acid solutions with iron catalyst resulted in gas accumulation and solid precipitation in the glass bottles. The pressurization and solid precipitation in a system with H 2 O 2 addition have been considered a potential hazard and a deliverabilitydeteriorating factor of Fenton s technique for subsurface remediation. On the other hand, no signs of gas accumulation or solid precipitation were observed in the citric acid batches, suggesting that the citric acid addition alleviated the adverse impacts which would have occurred with traditional sulfuric acid application Figure 1 shows the results of TCE removal with two acidified solutions (citric acid and sulfuric acid), and deionized water at varying H 2 O 2 additions (0 to 4%). Figure 1a depicts the case without iron catalysts in the system while Fig. 1b shows the result with the application of FeSO 4. The comparison of Fig. 1a and 1b shows that the addition

10 of FeSO 4 as a catalyst significantly improved the H 2 O 2 performance in removing TCE. Even in the deionized water batch (ph = 6) with iron, the removal rate reached nearly 100% with less than 1% H 2 O 2. The results showed that in the ph range of 3 (citric acid and sulfuric acid) to 6 (deionized water), the key component of TCE removal efficiency with H 2 O 2 oxidation was the iron catalyst, and citric acid acts as effectively as sulfuric acid does, suggesting the scavenging of OH by citric acid was not significant in the given condition Figures 1c and 1d show difference in TCE removal rates with the two acid solutions (citric acid and sulfuric acid), and deionized water when two filtered soil solution (Fig. 1c) and soil (Fig. 1d) were utilized as naturally available iron sources. In the filtered soil solutions (Fig. 1c) with TCE and acid solutions (citric acid and sulfuric), nearly 100% of TCE were removed with less than 1% of H 2 O 2 addition, while the deionized (acid-free) water needed 4% H 2 O 2 solution to completely remove TCE. This result indicates that water-soluble iron for the H 2 O 2 reaction was sufficiently available, and that acidic conditions enhanced the dissolution of soil soluble iron, resulting in higher efficiency in organic contaminant removals For Fig. 1d, two grams of soil samples was mixed with 25 ml organic compound solutions to assess the role of the local soil as a source of the iron catalyst as well as a scavenger for oxidants. Figure 1d shows the citric acid batches (ph = 3) had nearly 100% TCE removal by less than 2% H 2 O 2 solution, whereas the deionized water batches (ph = 7.6) had 64% organic compound removal by more than 3% H 2 O 2 solution. The removal rate was slower for the sulfuric acid solution than the citric acid, because the ph in the sulfuric acid solution after soil mixing was higher (ph = 6) than with the citric acid (ph =

11 ). The removal rates with the actual soil were lower compared with other cases of different iron sources (FeSO 4 or filtered soil solution), confirming the oxidant demand from oxidizable components of the soil reduced the removal efficiencies Figures 2a and 2b show the results from repeated tests of citric acid added Fenton s oxidation for cis-1,2-dce (Fig. 2a) and PCE (Fig. 2b). In this study, the chlorinated ethylenes generally showed decreasing susceptibility to H 2 O 2 oxidation in an order: DCE > TCE > PCE, which is consistent with the previous studies (e.g., Tang and Huang, 1997). PCE removal rates with the filtered soil solution were higher than that with FeSO 4 solution, suggesting that the concentration of iron mobilized by citric acid from the soil would be higher than that supplied by FeSO 4 solution (50 mg Fe 2+ L -1 ) Based on the results of the batch experiments, we found that (1) citric acid could act as an effective agent for lowering ph in soil solution to provide appropriate conditions for Fenton s reaction, (2) oxidant scavenging by citric acid was insignificant, and (3) availability of soluble soil iron was enhanced by adding acids The removal efficiencies with citric acid in the batch tests consistently showed that as the concentration of H 2 O 2 increases beyond 1%, the efficiencies of the Fenton s reaction in the organic contaminant removal decreased (see Figs. 1B, 1D, and 2), even though increasing removal efficiency was expected to have higher H 2 O 2 concentrations. This pattern of decreasing removal efficiencies with increasing concentration of H 2 O 2 (> 1%) was observed repeatedly in preliminary and subsequent duplicative tests with citric acid, while this phenomenon was not observed in tests involving the sulfuric acid and deionized water.

12 Possible explanations for this declining efficiency of organic contaminant removals could be a reaction between OH and H 2 O 2, and the formation of iron chelates between citric acid and iron species in the solutions. Potential reactions occurring in the citric acid-modified Fenton s system with excessive H 2 O 2 are listed in the Table 2. As shown in Eq. 1, Fenton s reaction initiates with reactions between Fe 2+ and H 2 O 2 with second-order rate constant of 63.0 M -1 s -1 (Gallard et al., 1998), which generates OH and Fe 3+. When the concentrations of H 2 O 2 and iron species are stoichiometrically balanced, iron species would play the role of catalyst. With excessive input of H 2 O 2 (> 1%), however, H 2 O 2 either competes for OH with organic contaminants (Table 2, Eq. 4), or reacts with Fe 3+ (Eq. 5) to generate hydroperoxyl radicals ( HO 2 ). As indicated by higher reaction rates, H 2 O 2 more actively reacts with OH (Eq. 4), and the excessive H 2 O 2 is quickly consumed to generate HO 2. Furthermore, the HO 2 preferably reacts with Fe 2+ to oxidize it to Fe 3+ (Eqs. 6 and 7) even though the reaction rate (Eq. 6) are slower than for OH oxidation of Fe 2+ to Fe 3+ (Eq. 8). Overall, the presence of excess H 2 O 2 would have Fe 3+ to be a dominant species in the Fenton s system and fast consumption of H 2 O 2, as previously reported by (Barb et al., 1951; Yoon et al., 1998) Citric acids form more stable iron chelates with Fe 3+ as indicated by a stability constant (log K) of 11.85, compared to Fe 2+ with log K = 3.2 (Furia, 1972). When Fe 3+ forms complexes with chelators, the activity of Fe 3+ to dissociate H 2 O 2 usually becomes low and it is inversely proportional to the stability of the chelations. The relations between the stability of chelates and the activity of iron species was presented by Sun and Pignatello (1992), which showed that the activity of iron chelates to transform 2,4-D decreases in order of tartaric > oxalic > citric, and the decreasing activity corresponds to

13 increasing stability constants (log K) of the three acids (log K = 7.49, 9.4, and 11.85, respectively) (Furia, 1972). Therefore, the strong chelates of citric acid Fe 3+ result in low activity of Fe 3+, inhibiting the iron species from getting reduced back into Fe 2+, and eventually Fe 3+ will be sequestered from the Fenton s catalytic cycle Based on the batch system of this study, an optimum ratio of [Fe 2+ ] and [H 2 O 2 ] at 1:330 (M:M) was estimated, and the ratio would become smaller with higher organic contaminant concentrations Column Experiments During the column experiments, three mechanisms of organic contaminant removal can occur: (1) volatile organic contaminant stripping with gas (mainly O 2 ) generated from H 2 O 2 decomposition, (2) liquid flushing of contaminants with injected H 2 O 2 solution, and (3) in situ chemical oxidation via Fenton s reaction. Mass balances were calculated to find contributions from the different removing mechanisms. Results are presented in Table 3 in terms of the relative contributions from the three potential mechanisms. The percentages of contaminants removed by Fenton s reaction were calculated by subtracting total mass of organic contaminants recovered by liquid and soil analysis from initial organic contaminant mass, based on assumptions that there were no other significant means of organic contaminant loss including biodegradation, irreversible sorption, and volatilization Liquid flushing was the most efficient organic contaminant removal mechanism, when CaCl 2 solution was injected without adding acidifying agents into the column (73% for DCE, and 74% for TCE, and 50% for PCE). The higher flushing removals of DCE and TCE result from the higher water solubility of those compounds. Calculated simply

14 by using Henry s constants based on assumption that the organic contaminants in gas were in equilibrium with those in liquid, we found that the percentages of organic contaminants removed by air stripping was negligibly small (< 1% of total organic compounds), which is quite different from the results of Chen et al. (2001) The total organic compound recovered by liquid and left in soil in the control columns reached 81 to 100%, which indicated compound mass losses due to other than H 2 O 2 reaction (biodegradation, volatilization loss, and other experimental losses) were less than 8% for TCE and PCE and less than 20% for DCE. The highest volatility of DCE may result in the larger loss. The total recovered mass in the acid-treated columns was less than 48%, meaning that more than 52% of mass were missing. This mass loss is about 2.5 times of what was measured from the corresponding control columns. This result suggested that the balance of contaminants masses were removed by the Fenton s reaction with acids, and the Fenton s oxidation with citric acid is as effective as sulfuric acid in destroying the organic contaminants. The citric acid columns showed 4 6% higher removal rates with the Fenton s reaction than the sulfuric acid columns. The higher efficiency by the citric acid columns might be caused by lower ph. The ph values in the liquid effluents were 3.5 for citric acid columns and 5.8 for sulfuric acid columns Overall, for 160 g of soil contaminated with organic compounds with a concentration range of 1,300 5,000 μgl -1 ( μg kg -1 soil), 25 ml of H 2 O 2 solution (3% H 2 O 2 ) was injected into acidified soil columns to achieve the organic contaminant removal rates of 50 to 65%. However, note that the experiments specifically address the efficiencies with respect to the reactants used and the chemistry of the soils collected for this study, and the results do not address site-specific hydrogeological

15 characteristics (e.g. heterogeneities in composition and permeability, cracks and layering) of this particular soil, which must be considered when applying any remediation technology Conclusions Citric acid has been examined for Fenton s reaction in terms of its possible role as an acidifying agent and a scavenger of hydroxyl radicals. Batch and column experiments performed with three types of organic contaminant demonstrate that the citric-acidmodified Fenton s reaction shows the organic contaminant removal efficiencies similar to the traditional sulfuric acid-aided Fenton s reaction. However, beyond a threshold concentration of H 2 O 2 with respect to the molar ratio with Fe 2+ (Fe 2+ : H 2 O 2 = 1: 330), the efficiency of H 2 O 2 in removal organic contaminants decreases A citric-acid-modified Fenton s reaction does not show significant gas accumulation and solid precipitations, which can cause flow path blockages, hamper continuous reagent injection, and would result in hazardous operational conditions for decontamination activity. Further studies on the reduction of gas accumulation and solid precipitation need to be performed to understand the mechanisms. In addition, subsequent to completion of Fenton s reaction, the residual citric acid could stimulate microbial activities near the injected area initiating reductive dechlorination. Long-term experiments need to be performed to verify the potential biological activities that could lead to subsequent biodegradation of contaminants. 333

16 Acknowledgment This article was developed at the Lawrence Berkeley National Laboratory, which is operated by the University of California for the U.S. Department of Energy under contract DE-AC02-05CH References Barb, W.G., Baxendale, J.H., George, P., Hargrave, K.R., Reactions of ferrous and ferric ions with hydrogen peroxide. II. The ferric ion reaction. T. Faraday Soc. 47, Chen G., Hoag, G.E., Chedda, P., Nadim, F., Woody, B.A., Dobbs, G.M., The mechanism and applicability of in situ oxidation of trichloroethylene with Fenton s reagent, J. Hazard. Mater. 87, Christensen, H., Sehested, K., Corfitzen, H., Reactions of hydroxyl radicals with hydrogen peroxide at ambient and elevated temperatures, J. Phys. Chem.-US. 86, Furia, T.E., CRC Handbook of Food Additives, CRC Press, Cleveland. Gallard H., de Laat, J., Legube, B., Influence du ph sur la vitesse d oxydation de composés organiques par Fe II /H 2 O 2. Mechanismes réactionnels et modélisation, New J. Chem Haber, F., Weiss, J., The catalytic decomposition of hydrogen peroxide by iron salts. P. Phys. Soc. Lond. A, 147, Hickey, W.J., Arnold, S.M., Harris, R.F., Degradation of atrazine by Fenton s reagent: Condition optimization and product quantification, Envion. Sci. Technol. 29, Kwan, W.P., Voelker, B.M., Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydrite, Environ. Sci. Technol. 36, Kong, S.-H., Watts, R.J., Choi, J.-H., Treatment of petroleum-contaminated soils using iron mineral catalyzed hydrogen peroxide, Chemosphere 37, Li, Y.C., Bachas, L.G., Bhattacharyya, D., Kinetic studies of trichlorophenol desctruction by chelate-based fenton reaction, Environ. Eng. Sci. 22, Lindsey, M.E., Xu, G., Lu, J., Tarr, M.A., Enhanced Fenton degradation of hydrophobic organics by simultaneous iron and pollutant complexation with cyclodexrins, Sci. Total Environ. 307,

17 Lindsey, M.E., Tarr, M.A., Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter, Environ. Sci. Technol. 34, Paciolla, M.D., Davies, G., Jansen, S.A., Generation of hydroxyl radicals from metal-loaded humic acids, Environ. Sci. Technol. 33, Pignatello, J.J., Dark and photoassisted Fe 3+ -catalysed degradation of chlorophenoxy herbicides by hydrogen peroxide, Environ. Sci. Technol. 26, Ravikumar, J.X., Gurol, M.D., Chemical oxidation of chlorinated organics by hydrogen peroxide in the presence of sand, Environ. Sci. Technol. 28, Rush, J.D., Bielski, B.H.J., Pulse radiolytic studies of the reactions of HO 2 /O - 2 with Fe(II) / Fe(III) ions. The reactivity of HO 2 /O - 2 with ferric ions and its implication on the occurrence of the Haber-Weiss reaction, J. Phys. Chem.-US. 89, Stuglik Z., Zagórski, Z.P., Pulse radiolysis of neutral ion (II) solutions: oxidation of ferrous ions by OH radicals, Radiat. Phys. Chem. 17, Sun, Y., Pignatello, J.J., Chemical treatment of pesticide wastes. Evaluation of Fe(III) chelates for catalytic hydrogen peroxide oxidation of 2,4-D at circumneutral ph, J. Agr. Food Chem. 40, Tang, W.Z., Huang, C.P., Stoichiometry of Fenton s reagent in the oxidation of chlorinated aliphatic organic pollutants, Environ. Sci. Technol. 18, Teel, A.L., Warberg, C.R., Atkinson, D.A., Watts, R.J., Comparison of mineral and soluble iron Fenton s catalyst for the treatment of trichloroethylene, Water Res. 35, Teel, A.L., Watts, R.J., Degradation of carbon tetrachloride by modified Fenton s reagent, J. Hazard. Mater., B94, Voelker, B.M., Sulzberger, B., Effects of fulvic acid on Fe(II) oxidation by hydrogen peroxide, Envion. Sci. Technol. 30, Walling, C., 1975, Fenton s reagent revisited, Accounts Chem. Res. 8, 125. Watts, R.J., Foget, M.K., Kong, S.-H., Teel, A.L., Hydrogen peroxide decomposition in model subsurface systems, J. Hazard. Mater. B69, Yoon, J., Lee, Y., Kim, S., Investigation of the reaction pathway of OH radicals produced by Fenton oxidation in the conditions of wastewater treatment, Water Sci. Technol. 44,

18 Tables and Figures Table 1. Soil Analysis Table 2. Second-order rate constants for Fe 3+ generation reactions with excessive H 2 O 2 Table 3. Mass balance (%) of volatile organic compounds in column experiments Figure 1. Batch test removal efficiencies (%) of TCE in three experiments (deionized, two acidified) with the varying concentrations of H 2 O 2. No iron catalyst was added in (a), and FeSO 4 7H 2 O in (b), filtered soil solution in (c), or two grams of soil in (d) was added as an iron source for catalysts. 24 h reaction time at 4 C Figure 2. Batch test removal efficiencies (%) of DCE (a) and PCE (b) in citric acid solutions with the varying iron sources and concentrations of H 2 O h reaction time at 4 C

19 Table 1. Soil Analysis Classification Silty Clay Soil ph 7.9 Alkalinity 1.56% Total Fe Content mg kg -1 Sorption Coefficient (K d, L kg -1 ) cis-dce: 0.48 TCE: 0.84 PCE: 1.66 Table 2. Second-order rate constants for Fe 3+ generation reactions with excessive H 2 O 2 H 2 O2 + OH HO2 + H 2O 1 k= M -1 s -1 (4) H 2O2 + Fe Fe + H + HO2 2 k= M -1 s -1 (5) HO 2 + Fe Fe + HO2 3 k= M -1 s -1 (6) HO 2 + Fe Fe + H + O2 4 k= M -1 s -1 (7) HO + Fe Fe + HO 5 k= M -1 s -1 (8) 1 Christensen et al. (1982), 2 Pignatello (1992), 3. Rush and Bielski (1985), 4 Haber and Weiss (1934), 5. Stuglik and Zagórski (1981) Table 3. Mass balance (%) of volatile organic compounds in column experiments DCE TCE PCE Mass Balance (%) CC CA SA CC CA SA CC CA SA Removed with Liquid Left in Soil Removed with Gas <1 <1 <1 <1 <1 <1 <1 <1 <1 Total VOC measured Unrecovered VOC < Calculated by subtracting the total VOC measured from 100%. VOC: volatile organic compound, DCE: cis 1,2-dichloroethylene, TCE: trichloroethylene, PCE: tetrachloroethylene, CC: CaCl M, CA: citric acid 0.5 M, SA: sulfuric acid 1 N.

20 a. H 2 O 2 Deionized Water Citric Acid Sulfuric Acid c. H 2 O 2 + Filtered Soil Solution TCE Removal (%) Deionized Water Citric Acid Sulfuric Acid b. H 2 O 2 + Fe 2+ d. H 2 O 2 + Soil TCE Removal (%) Deionized Water Citric Acid Sulfuric Acid Deionized Water Citric Acid Sulfuric Acid H 2 O 2 (%) H 2 O 2 (%) FIGURE 1

21 a. DCE DCE Removal (%) H 2 O 2 H 2 O 2 + Fe H 2 O 2 + Soil Solution H 2 O 2 + Soil b. PCE PCE Removal (%) H 2 O 2 H 2 O 2 + Fe H 2 O 2 + Soil Solution H 2 O 2 + Soil H 2 O 2 (%) FIGURE